Asphalt and process for manufacturing same



Unite ASPHALT AND rnocn ss non MANUFACTURING No Drawing. Application May 9, 1952, Serial No. 287,034

14 Claims. (Cl. 196-22) This invention concerns the treatment of residual oils and asphalts to provide improved asphaltic materials. In accordance with this invention, low molecular weight aliphatic ketones or aldehydes are employed to treat residual oils or asphalts to upgrade these materials to asphalts of desirable properties.

It is one object of this invention to provide a simple and eifective manner of converting residual petroleum oils to asphalts. As used herein, the term residual oil is employed to identify the liquid or semi-solid residues obtained from the destructive distillation of non-asphaltic petroleums, from the distillation of semi-asphaltic and asphaltic petroleums, from distillation of pressure tar, or from the fiuxing of harder residual asphalts with heavy distillates. The residual oil may be obtained for example, from a conventional vacuum distillation zone for petroleum crude oil. Such a residual oil may be recovered as a bottoms product from such a distillation system, and is generally characterized by a specific gravity of about 0.85 to 1.07 at 77 F. Normally, such a residual oil will have a fusing point as determined by the ring and ball method falling within the range of about 32 to 120 F. It is one object of this invention to provide a novel process for the upgrading of such residual oils to asphalts having softening points above about 120 F.

The present application is also of application to the treatment of asphalts derived from other processes in order to raise the melting point of such asphalts. For

example, asphalts may be obtained by the reduction of residual oils of the character identified. However, in

States Patent "ice hydes having about 1 to 8 carbon atoms, including formaldehyde or acetaldehyde are the preferred aldehydes. Ketones which may be employed are similarly low molecular weight aliphatic ketones having about 3 to 9 carbon atoms including acetone, methyl-ethyl ketone, methyl isopropyl ketone, methyl n-butyl ketone and diisobutyl ketone. Acetone or methyl-ethyl ketone are the preferred ketones for use in this invention. 7

The amount of the aldehyde or ketone to be employed in general varies from about 1% to 5% or more. For most purposes it is not necessary to employ more than 5% of the aldehyde or ketone, although quantities outside the ranges indicated may be employed if desired. A temperature above about 150 C. is required in order to secure suitable reaction of the treating re-agents with the asphaltic materials. In general, temperatures below 500 C. are to be employed. The treatment can be carried out at atmospheric pressures, although it is particularly preferred to conduct the treatment in a closed vessel permitting use of superatmospheric pressures. To some extent the time of reaction and the amount of treating agent required can be reduced by conducting the process at higher pressures.

The process does not depend upon the presenceof oxygen and the benefits of this invention are to some extent obviated if oxygen is permitted to intermingle with the reactants. Although the process is preferably carried out in the substantial absence of air, it is not necessary to employ special precautions to avoid the presence of 3.11.

The mechanism by which the ketones and aldehydes disclosed react with the asphaltic material is not presently understood.

The nature of this invention will be better understood by reference to the following data:

Example A residual oil of Venezuelan origin having a soften- TABLE I Venezuelan Venezuelan Typical Vacuun Typical Air Blown Residual fi ggi Reduced Vene- Asphalts Blown from 011 with 1% zuelen Asphalts Venezuelan Residual Oil Acetone Softening Point (R. an), F.

AS'IM D-36-26 116 180 154 162 187 150 162 1 180 187 Penetration, 77l100 /5 ASTM -49 98 18 19 12 6 22 19 14 12 Penetration 32l200 g 0" AS'IM D-5-49 20 5 5 3% 1% 8 5 4 4 Penetration, 115l50 g./5 ASTM D-5-4 Too Soft 49 70 43 19 80 57 38 33 Ductility, 77, cm. ASTM D-113-44..- 100+ 6.2 13 8% 0 y 16 5% 4 3% some cases it is not practical to obtain an asphalt having a high softening point by straight reduction of a residual oil. Consequently, the process of this invention is a desirable alternative process for the upgrading of low melting point asphalts to asphalts having a high melting point.

The objectives of this invention are attained by treating the asphaltic material to be processed with a minor portion of a low molecular weight aliphatic ketone or aldehyde. The ketone or aldehyde undergoes a reaction with the asphaltic material so as to substantially change the properties of the asphaltic material. Aldehydcs which may be employed are low molecular weight alde- It will be noted from this data that the treatment with acetone was successful in substantially raising the softening point of the asphalt. The 1% of acetone employed served to raise the softening point 64 F. The final ductility of this asphalt, that is, 6.2, for an asphalt of the indicated softening point is considered unusual since the ductility is higherthan that which would be obtained by air blowing or by vacuum reduction. Also at the indicated softening point the penetration at 77 F. is higher. The combination of high softening point, ductility, and penetration possessed by this asphalt qualifies the asphalt as a superior material for use in coating, laminating or saturating applications.

Example II In a second experiment formaldehyde was employed as the treating agent for an oxidized Venezuelan asphalt having a softening point of 244 F. This experiment was conducted to determine whether or not the softening point of this oxidized asphalt could be improved by the treatment of this invention. The formaldehyde was employed in the form of para-formaldehyde using 3% based onthe weight of the asphalt. The reaciionwas carried out in a closed vessel for one hour at a temperature of about 160 C. The propertiesof the'original asphalt and the treated asphalt are presented in Table'II below:

TABLE II Air Blown Asphalt Oxydized Treated Venezuelan with 3% Asphalt Paraforrnaldehyde Softening Point (R. & 13.), F. 245 276 Penetration, 77/100 g./5.. 6 5 Penetration, 32/200 g./60- 5 1 Penetration, 115l50 g./5.. 10 10 Ductility, 77, cm 0.9 0. 4

It will be noted from the data of Table II that again the formaldehyde was successful in raising the softening point of the asphalt. This was accomplished without any substantial change in theother asphalt properties listed.

Example III In a further experiment a residual oil having a softening point of 117 F. was treated with paraformaldehyde in a closed vessel for one hour at 150 C. A final product was obtained having a softening point of 130 F., a 77/100/ 5" penetration of 50, a 32/200/60" penetration of 15, and a 1l5/50/5" penetration of 250. The ductility at 77 F. was determined to be 100+. Again it will be seen fromthis data that the process of this invention was effective in upgrading the residual oil to an asphalt of desirable properties. The data of this experiment is summarized in Table III.

TABLE III Residual Venezuelan Oil Residual Treated Oil with 3% Paraformaldehyde Softening Point (R. & 13.), F.... 116 130 Penetration, 77/100 g./5" 98- 5O Penetration, 32l200 g./60. V 20 Penetration, 115l50 g./5'..... T00 Soft 250 Duetility, 77, cm.- -.----t..-.--- 100+ 100+ Example IV To establish the relationship between the softening point, penetration, and ductility proper-ties given, and properties required in non-staining asphalt applications, tests were determined to find the stain value of asphalts as treated in the foregoing experiments. The asphalt'employed inthis example was a Venezuelan residual oil treated with acetone having the properties'shown in Table IV. For comparative purposes,'tw0 different grades of Venezuelan oxidized asphalts were also tested for stain properties. Texas Stain Test, and the procedure and equipment used is reported in Industrialand Engineering Chemistry, 42, 2340-3 (1950); Oil Exudation Properties of Asphalts, E. C. Knowles, F. C. McCoy, H. E. Schmeyer, and C. E. Wilkinson. Briefly, the test consists of determining the number of cigarette papers which are stained by the oils exuding from a sample of asphalt. A high value indicates a poor asphalt. As described in' the literature, the test in volves 'placing a number "of sheets of cigarette paper in 4; time after which the number of stained papers are recorded. The results of these experiments are indicated in Table IV.

As shown by this data the acetone treated sample has less-tendency to stain than either the oxidized or 220/235 oxidized Colombian asphalts. The stain value of the acetone treated sample is lower than either (1) the lower softening point-higher penetration 160/ 180 oxidized; or (2) the higher softening point-lower penetration 220/ 235 oxidized asphalts. In addition the ductility of the treated asphalt is higher than either of the two asphalts.

What is claimed is:

1. A processfo'r improving the properties of a petroleum'asphaltic material in which the said asphaltic material is reacted ata temperature of at least about 150 C. withao'out 1 to 5% by weight of a compound selected from the group consisting-of C1 to C8 aliphatic aldehydes andCs to'C' aliphatic ketones.

2. A process for increasing the melting point of a petroleum residualoil in which the residual oil is reacted withabout" 1 to 5% by weight of a compound selected frorn'the group consisting of C1 to Cs aliphatic aldehyd'es" and 'C3 to C9 aliphatic ketones at a temperature above about 150 C.

3. The process defined by claim 2 in which the said reaction is conducted at superatmospheric pressures.

4. The process defined by claim 2 in which the said reaction is carried out in the absence of oxygen.

5. The process defined by claim 1 wherein said compound is formaldehyde.

6. The process defined by claim 1 wherein said compound is acetaldehyde.

7. The process defined'by claim 1 wherein said compound is acetone.

8; The process defined by claim 1 wherein said compound is methylethyl ketone.

9. A process for improving the properties of a petroleum asphaltic material, including increasing the softening point thereof, in which said asphaltic material is reacted with about 1 to 5% of formaldehyde at a temperature in the range of about 150 to 500 C. in the substantial absence of oxygen.

10. The process defined by claim 9 wherein said asphalti'c'material is'an oxidized asphalt obtained from a Venezuelan petroleum oil and has a softening point of about 244 F. I

11. The process defined by claim 9 wherein said asphaltic material is a Venezuelan residual oil having a softening point of about 117 F.

12-. A process for improving the properties of a petroleum asphaltic material, including increasing the softening point thereof, in which said asphaltic material is reacted with about 1 to 5% of acetone at a temperature in the range 'ofabout l50 to 500 C. in the substantial absence of oxygen.

13. The processdefined'by claim 12 wherein said asphaltic'material'- is a Venezuelan residual oil having a softeningpoint of about 117 d F.

14'. As a new composition of matter a petroleum derivative-prepared by reacting a material selected from the group' consisting of asphaltic material and residual oil with'about 1% to 5% by weight of an aliphatic carbonyl 5 compound having no more than 9 carbon atoms at 21 2,115,496 temperature of at least about 150 C. 2,465,960

References Cited in the file of this patent UNITED STATES PATENTS 5 486,022 1,868,879 Broadhead et a1. July 26, 1932 683,848 2,095,190 Heuscher Oct. 5, 1937 6 Mater Apr. 26, 1938 Berge Mar. 29, 1949 FOREIGN PATENTS Germany Nov. 9, 1929 Germany Nov. 20, 1939 

1. A PROCESS FOR IMPROVING THE PROPERTIES OF A PETROLEUM ASPHALITC MATERIAL IN WHICH THE SAID ASPHALTIC MATERIAL IS REACTED AT A TEMPERATURE OF AT LEAST ABOUT 150* C. WITH ABOUT 1 TO 5% BY WEIGHT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF C1 TO C8 ALIPHATIC ALDEHYDES AND C3 AND C9 ALIPHATIC KETONES.
 14. AS A NEW COMPOSITION OF MATTER A PETROLEUM DERIVATIVE PREPARED BY REACTING A MATERIAL SELECTED FROM THE GROUP CONSISTING OF ASPHALTIC MATERIAL AND RESIDUAL OIL WITH ABOUT 1% TO 5% BY WEIGHT OF AN ALIPHATIC CARBONYL COMPOUND HAVING NO MORE THAN 9 CARBON ATOMS AT A TEMPERATURE OF AT LEAST ABOUT 150* C. 